CN104787751B - A kind of graphene powder and preparation method thereof - Google Patents
A kind of graphene powder and preparation method thereof Download PDFInfo
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- CN104787751B CN104787751B CN201410020760.9A CN201410020760A CN104787751B CN 104787751 B CN104787751 B CN 104787751B CN 201410020760 A CN201410020760 A CN 201410020760A CN 104787751 B CN104787751 B CN 104787751B
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Abstract
The invention provides a kind of preparation method of graphene powder, comprise the following steps：A, graphite oxide and dispersant reacted, obtain intermediate product, the dispersant includes ammonium salt；B, the intermediate product is heat-treated, obtains graphene powder.In the present invention, dispersant can weaken degree of intimate contact between oxidized graphite flake layer, and the graphene powder reunion degree for obtaining the present invention is low, dispersed preferable；And the gas that the dispersant in the present invention is produced in heat treatment process by thermal decomposition peels off graphite oxide, the reunion degree for the graphene powder that the present invention is provided further is reduced, the present invention is obtained dispersed preferably graphene powder.Compared with prior art, the present invention need not carry out spray drying treatment and can obtain dispersed preferably graphene powder, therefore preparation method efficiency high, the energy consumption of the graphene powder of the invention provided are low, available for large-scale production graphene powder.
Description
Technical field
The present invention relates to technical field of graphene, more particularly to a kind of graphene powder and preparation method thereof.
Background technology
Graphene（Graphene）It is a kind of individual layer laminated structure being made up of carbon atom, only one of which carbon atom thickness
Two-dimensional material.Graphene has all shown excellent performance at many aspects, such as graphene is almost fully transparent, only inhales
The light of receipts 2.3%, its translucency is very good；The thermal conductivity factor of graphene is up to 5300W/mK, higher than CNT and Buddha's warrior attendant
Stone；Electron mobility under graphene normal temperature is more than 15000cm2/ Vs, higher than CNT and silicon crystal；The electricity of graphene
Resistance rate only has 10-6Ω cm, it is lower than copper or silver, it is the minimum material of current resistivity；In addition graphene is also most thin at present
But most hard material.Graphene is prepared into the application that powder is more beneficial for graphene, such as graphene powder can be used as high score
The additive of sub- material, improves the electric property and mechanical strength of high polymer material, and graphene powder has before wide application
Scape.
At present, graphene powder can be prepared using a variety of methods, such as mechanical stripping method, oxidation-reduction method, outside crystal
Epitaxial growth, chemical vapour deposition technique, organic synthesis method and stripping CNT method etc..In these methods, oxidation-reduction method
The realization with low cost and easy of graphene powder is prepared, is the best approach for preparing graphene powder.
The Chinese patent of Application No. 201310200469.5 discloses a kind of preparation method of graphene powder, by graphite
It is added in the mixed solution containing oxidant and intercalator and stirs, obtained mixed solution is carried out ultrasonically treated same
When be passed through helium, form the graphite intercalation compound of intercalator and helium molecule intercalation；Obtained graphite intercalation compound is filtered,
It is heat-treated in atmosphere after washing, drying；Graphite intercalation compound after heat treatment is scattered in organic solvent, holding
Continuous be passed through under conditions of helium carries out ultrasonic stripping again；Graphite intercalation compound after ultrasound stripping again is centrifuged, precipitated,
Filtering, washing, drying, you can obtain graphene powder.The reunion degree for the graphene powder that this method is obtained is higher, makes stone
Black alkene powder it is dispersed poor, be unfavorable for the application of graphene powder, therefore prepare the graphene powder of good dispersion turning into
The focus studied at present.
The Chinese patent of Application No. 201010593157.1 discloses a kind of preparation method of graphene powder, will aoxidize
Graphite uniformly peels off into graphene oxide aaerosol solution；The graphene oxide prepared is set to suspend using spray drying technology molten
Liquid mist, graphite oxide powder is obtained to remove the solvent in the aaerosol solution；In inert atmosphere or the guarantor of reducing atmosphere
Under shield, obtained graphite oxide powder is carried out to be heat-treated without expansion, graphene powder is obtained.Prior art is using spray drying
Although technology can be obtained, reunion degree is relatively low, dispersed preferable graphene powder, the effect of this spray drying technology
Rate is low, energy consumption is big, and the large-scale production of graphene powder is not utilized.
The content of the invention
In view of this, it is an object of the invention to provide a kind of graphene powder and preparation method thereof, what the present invention was provided
The reunion degree of graphene powder is relatively low, dispersed preferable, and the preparation method energy consumption of the graphene powder of the invention provided
Low, efficiency high, available for large-scale production graphene powder.
The invention provides a kind of preparation method of graphene powder, comprise the following steps：
A, graphite oxide and dispersant reacted, obtain intermediate product, the dispersant includes ammonium salt；
B, the intermediate product is heat-treated, obtains graphene powder.
It is preferred that, the mass ratio of graphite oxide and dispersant is 1 in the step a:（1~10）.
It is preferred that, dispersant includes the one or more in ammonium sulfate, ammonium carbonate and ammonium hydrogen carbonate in the step a.
It is preferred that, the reaction temperature reacted in the step a is 15 DEG C~40 DEG C；
The reaction time reacted in the step a is 24 hours~96 hours.
It is preferred that, the preparation method of graphite oxide is in the step a：
Graphite is subjected to oxidation reaction, reaction solution is obtained；
The reaction solution is mixed with alkali compounds, the reaction product in the reaction solution is flocculated, obtains oxygen
Graphite.
It is preferred that, the alkali compounds includes the one or more in sodium carbonate, sodium hydroxide and potassium hydroxide.
It is preferred that, the temperature being heat-treated in the step b is 80 DEG C~800 DEG C；
The time being heat-treated in the step b is 0.5min~30min.
It is preferred that, the step b is specially：
The intermediate product is subjected to pre-dried, predrying product is obtained；
The predrying product is heat-treated, graphene powder is obtained.
It is preferred that, the temperature of the pre-dried is 40 DEG C~80 DEG C；
The time of the pre-dried is 12 hours~96 hours.
The invention provides a kind of graphene powder, the graphene powder is prepared into by above-mentioned technical proposal methods described
Arrive.
The invention provides a kind of preparation method of graphene powder, comprise the following steps：A, by graphite oxide with it is scattered
Agent is reacted, and obtains intermediate product, and the dispersant includes ammonium salt；B, the intermediate product is heat-treated, obtains stone
Black alkene powder.In the present invention, dispersant can reduce the moisture in graphite oxide, it is to avoid graphene oxide is in dehydration
Stronger capillary force is produced in journey, weakens the degree being in close contact between graphene oxide layer, the stone for obtaining the present invention
The reunion degree of black alkene powder is relatively low, dispersed preferable；And the dispersant in the present invention is heated during heat treatment and divided
Solution produces substantial amounts of gas, and the gas of generation can peel off graphite oxide, further reduces the graphene that the present invention is provided
The reunion degree of powder, makes the present invention obtain dispersed preferably graphene powder.Compared with prior art, the present invention need not enter
Row spray drying treatment can prepare dispersed preferably graphene powder, therefore the graphene powder that provides of the present invention
The low, efficiency high of preparation method power consumption, available for large-scale production graphene powder.
In addition, the decomposition temperature of the dispersant in the present invention is relatively low, the present invention need not carry out high-temperature heat treatment and can remove
Dispersant, is conducive to controlling the obtained degree of oxidation of graphene powder in heat treatment process, the present invention is prepared oxygen
The controllable graphene powder of change degree.
Test result indicates that, the lamella stacking degree for the graphene powder that the present invention is provided is relatively low, and dispersiveness is preferably；This hair
The carbon oxygen mass ratio of the graphene powder of bright offer is（0.5~2）:1, the present invention can prepare the controllable graphite of degree of oxidation
Alkene powder.
Brief description of the drawings
Fig. 1 is the ESEM for the graphene powder that the embodiment of the present invention 1 is obtained（SEM）Figure.
Embodiment
The invention provides a kind of preparation method of graphene powder, comprise the following steps：
A, graphite oxide and dispersant reacted, obtain intermediate product, the dispersant includes ammonium salt；
B, the intermediate product is heat-treated, obtains graphene powder.
In the present invention, dispersant can reduce the moisture in graphite oxide, it is to avoid graphene oxide layer is being lost
Stronger capillary force is produced during water, weakens the degree being in close contact between graphene oxide layer, obtains the present invention
Graphene powder reunion degree it is relatively low, it is dispersed preferably；And the dispersant in the present invention during heat treatment by
Thermal decomposition produces substantial amounts of gas, and the gas of generation can peel off graphite oxide, further reduces the stone that the present invention is provided
The reunion degree of black alkene powder, makes the present invention obtain dispersed preferably graphene powder.Compared with prior art, nothing of the present invention
Spray drying treatment, which need to be carried out, can prepare dispersed preferably graphene powder, therefore the Graphene powder that the present invention is provided
The preparation method energy consumption of body is low, efficiency high, available for large-scale production graphene powder.In addition, dispersant in the present invention
Decomposition temperature is relatively low, and the present invention need not carry out high-temperature heat treatment and can remove dispersant, is conducive to controlling in heat treatment process
The degree of oxidation of obtained graphene powder, makes the present invention prepare the controllable graphene powder of degree of oxidation.
The present invention is reacted graphite oxide with dispersant, obtains intermediate product, preferably by graphite oxide it is scattered afterwards and
Dispersant is reacted, and obtains intermediate product.The present invention does not have special limitation to the scattered method, using this area skill
Dispersion technology scheme known to art personnel, graphite oxide is preferably dispersed in water by the present invention to be reacted with dispersant,
Obtain intermediate product.In the present invention, the reaction temperature of the reaction is preferably 15 DEG C~40 DEG C, more preferably 20 DEG C~30
℃；The reaction time of the reaction is preferably 24 hours~96 hours, and more preferably 48 hours~72 hours, most preferably 50 is small
When~65 hours.In the present invention, the mass ratio of the graphite oxide and dispersant is preferably 1:（1~10）, more preferably 1:
（2~8）, most preferably 1:（3~7）.
In the present invention, the granularity of the graphite oxide is preferably 2 μm~100 μm, more preferably 10 μm~80 μm, optimal
Elect 20 μm~60 μm as.In the present invention, the graphite oxide can be bought by market and be obtained, and can also make by the following method
It is standby to obtain：
Graphite is subjected to oxidation reaction, reaction solution is obtained；
The reaction solution is mixed with alkali compounds, the reaction product in the reaction solution is flocculated, obtains oxygen
Graphite.
Graphite is preferably carried out oxidation reaction by the present invention, obtains reaction solution；More preferably in the presence of acid and oxidant,
Graphite is subjected to oxidation reaction, reaction solution is obtained, the acid includes fuming nitric aicd, and the oxidant includes chlorate；It is optimal
Choosing first mixes above-mentioned acid and graphite, and above-mentioned oxidant is added into obtained mixture and carries out oxidation reaction, reaction is obtained molten
Liquid.The present invention does not have special limitation to the method for the mixing, using hybrid technology scheme well known to those skilled in the art
；The present invention mixes graphite, acid and oxidant preferably under conditions of stirring, carries out oxidation reaction, obtains reaction solution.
In the present invention, the reaction temperature of the oxidation reaction is preferably 60 DEG C~80 DEG C, more preferably 65 DEG C~75 DEG C；The oxidation
The reaction time of reaction is preferably 22 hours~96 hours, more preferably 30 hours~72 hours, most preferably 35 hours~48
Hour.
The present invention does not have special limitation to the species of the graphite, and the graphite both can be native graphite, can also
Can also be Delanium for expanded graphite.In the present invention, the granularity of the graphite is preferably 2 μm~100 μm, more preferably
For 10 μm~80 μm, most preferably 20 μm~60 μm.The present invention originates without special limitation to the graphite, using this area
The graphite of mentioned kind known to technical staff, can such as be bought by market and obtained.
Graphite preferably in the presence of acid and oxidant, is carried out oxidation reaction, obtains reaction solution by the present invention.In this hair
In bright, the acid includes fuming nitric aicd, and the mass concentration of the fuming nitric aicd is preferably 86%~98%, more preferably 90%~
95%.The present invention, without special limitation, can be bought by market and be obtained to the source of the fuming nitric aicd, it would however also be possible to employ this
The compound method of fuming nitric aicd known to art personnel is prepared and obtained.
In the present invention, the acid preferably also includes the one or more in phosphoric acid and the concentrated sulfuric acid, more preferably also includes phosphorus
One kind in acid and the concentrated sulfuric acid.In the present invention, when mixed acid of the acid for fuming nitric aicd and phosphoric acid, the fuming nitric aicd
Mass ratio with phosphoric acid is preferably（2.5~5.5）:1, more preferably（3.5~5）:1；When the acid is fuming nitric aicd and dense sulphur
During the mixed acid of acid, the mass ratio of the fuming nitric aicd and the concentrated sulfuric acid is preferably（5~25）:1, more preferably（10~20）:1.
In the present invention, the mass concentration of the phosphoric acid is preferably 80%~90%, and more preferably 82%~88%.The present invention is right
The source of the phosphoric acid can be bought by market and be obtained, it would however also be possible to employ those skilled in the art know without special limitation
Preparation phosphoric acid method prepare obtain.In the present invention, the mass concentration of the concentrated sulfuric acid is preferably 70%~98%, more preferably
For 85%~95%.The present invention, without special limitation, can be bought by market and be obtained, can also adopted to the source of the concentrated sulfuric acid
Prepared and obtained with the compound method of the concentrated sulfuric acid well known to those skilled in the art.
In the present invention, the oxidant includes chlorate, and the chlorate is preferably one in sodium chlorate and potassium chlorate
Plant or two kinds.The present invention originates without special limitation to the chlorate, using well known to those skilled in the art above-mentioned
The chlorate of species, can such as be bought by market and obtained.
In the present invention, the oxidant preferably also includes potassium permanganate.In the present invention, the chlorate and permanganic acid
The mass ratio of potassium is preferably（4~9）:1, more preferably（5~8）:1.The present invention is not special to the source of the potassium permanganate
Limitation, such as can by market buy obtain.
In the present invention, the mass ratio of the graphite, acid and oxidant is preferably 1:（30~60）:（10~20）, it is more excellent
Elect 1 as:（35~55）:（12~18）.
After the completion of the oxidation reaction, the present invention preferably stands obtained reaction solution.In the present invention, it is described to stand
Time be preferably 24 hours~96 hours, more preferably 48 hours~72 hours.The present invention does not have to the method for the standing
Special limitation, using standing technical scheme well known to those skilled in the art.
Obtain after reaction solution, the present invention preferably mixes the reaction solution with alkali compounds, make the reaction molten
Reaction product flocculation in liquid, obtains graphite oxide；More preferably alkali compounds is added in the reaction solution, made described
Reaction product flocculation in reaction solution, obtains graphite oxide.In the present invention, the consumption of the alkali compounds preferably makes institute
The pH value for stating reaction solution reaches 10~13, more preferably up to 11~12.In the present invention, the alkali compounds is preferably carbon
One kind in one or more in sour sodium, sodium hydroxide and potassium hydroxide, more preferably sodium hydroxide and potassium hydroxide or two
Kind.
In the present invention, the alkali compounds can make the reaction product in the reaction solution flocculate, and be aoxidized
Graphite；The present invention preferably washs obtained graphite oxide to neutrality.The present invention does not have special limit to the method for the washing
System, using washing technology scheme well known to those skilled in the art；In the present invention, the reagent of the washing is preferably
Water, more preferably deionized water.The present invention is first using the alkali compounds described in above-mentioned technical proposal by the reaction solution
Reaction product flocculation, obtain graphite oxide；Obtained graphite oxide is washed again, the time of washing can be saved, carried
The efficiency of height washing.
In the present invention, the dispersant includes ammonium salt.In the present invention, the ammonium salt preferably includes ammonium sulfate, carbonic acid
One or more in ammonium and ammonium hydrogen carbonate, more preferably including one kind in ammonium carbonate and ammonium hydrogen carbonate.In the present invention, it is described
Dispersant can reduce the moisture in graphite oxide, it is to avoid be produced between graphene oxide layer in dehydration process stronger
Capillary force, weaken the degree that is in close contact between graphene oxide layer, make the group for the graphene powder that the present invention obtains
Poly- degree is relatively low, dispersed preferable.
Obtain after intermediate product, the intermediate product is heat-treated by the present invention, obtains graphene powder；It is preferred that by institute
State intermediate product and carry out pre-dried, obtain predrying product；The predrying product is heat-treated, graphene is obtained
Powder.In the present invention, the temperature of the heat treatment is preferably 80 DEG C~800 DEG C, more preferably 100 DEG C~700 DEG C, most preferably
For 200 DEG C~600 DEG C.In the present invention, the time of the heat treatment is preferably 0.5min~30min, and more preferably 1min~
20min, most preferably 5min~10min.In the present invention, the dispersant described in above-mentioned technical proposal is at a lower temperature
It can be thermally decomposed, therefore the present invention can remove the dispersant in above-mentioned intermediate product under relatively low heat treatment temperature, obtain
To graphene powder.
The intermediate product is preferably carried out pre-dried by the present invention, obtains predrying product；By the predrying production
Thing is heat-treated, and obtains graphene powder.In the present invention, the temperature of the pre-dried is preferably 40 DEG C~80 DEG C,
More preferably 50 DEG C~60 DEG C；The time of the pre-dried is preferably 12 hours~96 hours, more preferably 24 hours~
60 hours, most preferably 30 hours~50 hours.In the present invention, the pre-dried is preferably vacuum drying treatment.
Obtain after predrying product, the predrying product is preferably heat-treated by the present invention, obtains graphene powder.
In the present invention, the temperature and time of the heat treatment is consistent with the temperature and time being heat-treated described in above-mentioned technical proposal,
This is repeated no more.
In the present invention, the dispersant described in above-mentioned technical proposal can be thermally decomposed during heat treatment, and
The product noresidue that the dispersant is thermally decomposed, makes the impurity of obtained graphene powder of the invention less；And described point
Powder produces substantial amounts of gas in by thermal decomposition process, and the gas of generation can be peeled off above-mentioned intermediate product, further subtract
The reunion degree for the graphene powder that the weak present invention is obtained, makes the present invention obtain dispersed preferably graphene powder.
In the present invention, the temperature that different oxygen-containing functional groups are thermally decomposed in above-mentioned graphite oxide is different, and the present invention passes through
The graphene powder of different degree of oxidations can be obtained by controlling the temperature and time of above-mentioned heat treatment.Due to scattered in the present invention
The decomposition temperature of agent is relatively low, and this law is bright to be heat-treated using lower temperature and short period to the intermediate product, this
Sample can obtain the higher graphene powder of degree of oxidation, and abundant oxygen-containing functional group is contained simultaneously in the surface of this graphene powder
With larger specific surface area, make it that there is unique advantage in terms of catalysis and energy storage；The present invention can also be to the centre
Product carries out higher temperature and the heat treatment of long period, can so obtain the less graphene powder of degree of oxidation, this
The surfacing of graphene powder, defect is less, with preferable crystallinity.The need for the present invention can be according to actual conditions, adjust
The temperature and time of whole above-mentioned heat treatment, prepares the controllable graphene powder of degree of oxidation.
The invention provides a kind of graphene powder, the graphene powder is prepared as the method described in above-mentioned technical proposal
Obtain, the preparation method at this to the graphene powder is repeated no more.The lamella for the graphene powder that the present invention is provided is stacked
Degree is relatively low, and dispersiveness is preferably.
The present invention tests the dispersiveness for the graphene powder that the present invention is provided, test by scanning electron microscope analysis
As a result it is that the graphene powder lamella stacking degree that the present invention is provided is relatively low, with preferable dispersiveness.The present invention passes through element
The method of analysis test analyzes the carbon oxygen mass ratio for the graphene powder that the present invention is provided, and the test result present invention is provided
The carbon oxygen mass ratio of graphene powder is（0.5~2）:1, the present invention can prepare the controllable graphene powder of degree of oxidation.
The invention provides a kind of preparation method of graphene powder, comprise the following steps：A, by graphite oxide with it is scattered
Agent is reacted, and obtains intermediate product, and the dispersant includes ammonium salt；B, the intermediate product is heat-treated, obtains stone
Black alkene powder.In the present invention, dispersant can reduce the moisture in graphite oxide, it is to avoid graphene oxide is in dehydration
Stronger capillary force is produced in journey, weakens the degree being in close contact between graphene oxide layer, the stone for obtaining the present invention
The reunion degree of black alkene powder is relatively low, dispersed preferable；And the dispersant in the present invention is heated during heat treatment and divided
Solution produces substantial amounts of gas, and the gas of generation can peel off graphite oxide, further reduces the graphene that the present invention is provided
The reunion degree of powder, makes the present invention obtain dispersed preferably graphene powder.Compared with prior art, the present invention need not enter
Row spray drying treatment can prepare dispersed preferably graphene powder, therefore the graphene powder that provides of the present invention
The low, efficiency high of preparation method power consumption, available for large-scale production graphene powder.In addition, the decomposition of the dispersant in the present invention
Temperature is relatively low, and the present invention need not carry out high-temperature heat treatment and can remove dispersant, be conducive to controlling to obtain in heat treatment process
Graphene powder degree of oxidation, make the present invention prepare the controllable graphene powder of degree of oxidation.
The graphene powder provided to further appreciate that the present invention with reference to embodiment the present invention and its preparation side
Method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
In the following embodiments, used graphite oxide, native graphite, expanded graphite, fuming nitric aicd, phosphoric acid, dense sulphur
Acid, sodium chlorate, potassium chlorate, potassium permanganate, sodium carbonate, sodium hydroxide, potassium hydroxide, ammonium sulfate, ammonium carbonate and ammonium hydrogen carbonate are equal
For commercial goods.
Embodiment 1
Under conditions of stirring, 10g granularities are first mixed for 2 μm of native graphite and 200mL fuming nitric aicd, to obtaining
Mixture in add 100g sodium chlorate after the oxidation reaction of 96 hours is carried out at 60 DEG C, obtain reaction solution.
After above-mentioned reaction solution is stood into 24 hours, sodium carbonate is added into the reaction solution, makes the reaction solution
PH value be 11, by the reaction solution reaction product flocculate, obtain graphite oxide.
Above-mentioned graphite oxide is washed with water to after neutrality, by the graphite oxide and ammonium hydrogen carbonate in mass ratio 1:1
Ratio is dispersed in water, and is then reacted 24 hours at 15 DEG C, is obtained intermediate product.By above-mentioned intermediate product in 40 DEG C, vacuum
Under the conditions of drying process 96 hours, obtain predrying product；The predrying product is heat-treated 30min at 80 DEG C, obtained
Graphene oxide powder.
The graphene powder that the present invention obtains embodiment 1 is scanned electron-microscopic analysis test, and test result is such as
Shown in Fig. 1, Fig. 1 is the ESEM for the graphene powder that the embodiment of the present invention 1 is obtained（SEM）Figure, as seen from Figure 1, this
The lamella stacking degree for the graphene powder that inventive embodiments 1 are obtained is relatively low, and dispersiveness is preferably.The present invention obtains embodiment 1
Graphene powder carry out elementary analysis test, test result is the carbon oxygen matter of graphene powder that the embodiment of the present invention 1 is obtained
Amount is than being 1:2.
Embodiment 2
By the graphite oxide and ammonium carbonate in mass ratio 1 that granularity is 100 μm:10 ratio is dispersed in water, then 40
Reacted 96 hours at DEG C, obtain intermediate product.
Processing 12 hours is dried in above-mentioned intermediate product under 80 DEG C, vacuum condition, predrying product is obtained；By institute
State predrying product and be heat-treated 0.5min at 800 DEG C, obtain graphene powder.According to the method described in embodiment 1 to implementing
The dispersiveness and carbon oxygen mass ratio for the graphene powder that example 2 is obtained are detected that testing result is that the embodiment of the present invention 2 is obtained
The lamella of graphene powder stack that degree is relatively low, preferably, the carbon oxygen mass ratio of graphene powder is 2 to dispersiveness:1.
Embodiment 3
Under conditions of stirring, by phosphoric acid of the 10g granularities for 10 μm of expanded graphite, 240mL fuming nitric aicd and 60mL
First mix, the oxidation reaction of the progress 30 hours at 80 DEG C after 200g potassium chlorate is added into obtained mixture, obtain anti-
Answer solution.
After above-mentioned reaction solution is stood into 96 hours, sodium hydroxide is added into the reaction solution, makes the reaction molten
The pH value of liquid is 13, and the reaction product in the reaction solution is flocculated, graphite oxide is obtained.
Above-mentioned graphite oxide is washed with water to after neutrality, by the graphite oxide and ammonium hydrogen carbonate in mass ratio 1:5
Ratio is dispersed in water, and is then reacted 48 hours at 20 DEG C, is obtained intermediate product.
Processing 12 hours is dried in above-mentioned intermediate product under 50 DEG C, vacuum condition, predrying product is obtained；By institute
State predrying product and be heat-treated 1min at 100 DEG C, obtain graphene powder.
The dispersiveness and carbon oxygen mass ratio of the graphene powder obtained according to the method described in embodiment 1 to embodiment 3 are entered
Row detection, testing result is that the lamella stacking degree for the graphene powder that the embodiment of the present invention 3 is obtained is relatively low, and dispersiveness is preferable,
The carbon oxygen mass ratio of graphene powder is 1:1.
Embodiment 4
Under conditions of stirring, by dense sulphur of the 10g granularities for 20 μm of expanded graphite, 200mL fuming nitric aicd and 10mL
Acid is first mixed, and is carried out after 96g potassium chlorate and 24g potassium permanganate are added into obtained mixture at 65 DEG C 22 hours
Oxidation reaction, obtains reaction solution.
After above-mentioned reaction solution is stood into 30 hours, potassium hydroxide is added into the reaction solution, makes the reaction molten
The pH value of liquid is 12, and the reaction product in the reaction solution is flocculated, graphite oxide is obtained.
Above-mentioned graphite oxide is washed with water to after neutrality, by the graphite oxide and ammonium sulfate in mass ratio 1:3 ratio
Example is dispersed in water, and is then reacted 72 hours at 23 DEG C, is obtained intermediate product.
Processing 20 hours is dried in above-mentioned intermediate product under 55 DEG C, vacuum condition, predrying product is obtained；By institute
State predrying product and be heat-treated 3min at 200 DEG C, obtain graphene powder.
The dispersiveness and carbon oxygen mass ratio of the graphene powder obtained according to the method described in embodiment 1 to embodiment 4 are entered
Row detection, testing result is that the lamella stacking degree for the graphene powder that the embodiment of the present invention 4 is obtained is relatively low, and dispersiveness is preferable,
The carbon oxygen mass ratio of graphene powder is 1:1.5.
Embodiment 5
Under conditions of stirring, by dense sulphur of the 10g granularities for 30 μm of native graphite, 384mL fuming nitric aicd and 16mL
Acid is first mixed, and is carried out 23 hours at 68 DEG C after 126g potassium chlorate and 14g potassium permanganate are added into obtained mixture
Oxidation reaction, obtain reaction solution.
After above-mentioned reaction solution is stood into 40 hours, potassium hydroxide is added into the reaction solution, makes the reaction molten
The pH value of liquid is 12, and the reaction product in the reaction solution is flocculated, graphite oxide is obtained.
Above-mentioned graphite oxide is washed with water to after neutrality, by the graphite oxide and ammonium sulfate in mass ratio 1:8 ratio
Example is dispersed in water, and is then reacted 36 hours at 25 DEG C, is obtained intermediate product.
Processing 30 hours is dried in above-mentioned intermediate product under 65 DEG C, vacuum condition, predrying product is obtained；By institute
State predrying product and be heat-treated 15min at 120 DEG C, obtain graphene powder.
The dispersiveness and carbon oxygen mass ratio of the graphene powder obtained according to the method described in embodiment 1 to embodiment 5 are entered
Row detection, testing result is that the lamella stacking degree for the graphene powder that the embodiment of the present invention 5 is obtained is relatively low, and dispersiveness is preferable,
The carbon oxygen mass ratio of graphene powder is 1:1.76.
Embodiment 6
By the graphite oxide and ammonium carbonate in mass ratio 1 that granularity is 2 μm:6 ratio is dispersed in water, then at 30 DEG C
Reaction 60 hours, obtains intermediate product.
Processing 40 hours is dried in above-mentioned intermediate product under 70 DEG C, vacuum condition, predrying product is obtained；By institute
State predrying product and be heat-treated 8min at 500 DEG C, obtain graphene powder.
The dispersiveness and carbon oxygen mass ratio of the graphene powder obtained according to the method described in embodiment 1 to embodiment 6 are entered
Row detection, testing result is that the lamella stacking degree for the graphene powder that the embodiment of the present invention 6 is obtained is relatively low, and dispersiveness is preferable,
The carbon oxygen mass ratio of graphene powder is 1:1.5.
Embodiment 7
By the graphite oxide and ammonium sulfate in mass ratio 1 that granularity is 60 μm:6 ratio is dispersed in water, then at 35 DEG C
Lower reaction 72 hours, obtains intermediate product.
Processing 50 hours is dried in above-mentioned intermediate product under 75 DEG C, vacuum condition, predrying product is obtained；By institute
State predrying product and be heat-treated 10min at 600 DEG C, obtain graphene powder.
The dispersiveness and carbon oxygen mass ratio of the graphene powder obtained according to the method described in embodiment 1 to embodiment 7 are entered
Row detection, testing result is that the lamella stacking degree for the graphene powder that the embodiment of the present invention 7 is obtained is relatively low, and dispersiveness is preferable,
The carbon oxygen mass ratio of graphene powder is 1:1.
Embodiment 8
Under conditions of stirring, by phosphoric acid of the 10g granularities for 80 μm of native graphite, 180mL fuming nitric aicd and 60mL
First mix, carried out after 150g sodium chlorate and 30g potassium permanganate are added into obtained mixture at 72 DEG C 26 hours
Oxidation reaction, obtains reaction solution.
After above-mentioned reaction solution is stood into 50 hours, sodium carbonate is added into the reaction solution, makes the reaction solution
PH value be 11, by the reaction solution reaction product flocculate, obtain graphite oxide.
Above-mentioned graphite oxide is washed with water to after neutrality, by the graphite oxide and ammonium hydrogen carbonate in mass ratio 1:9
Ratio is dispersed in water, and is then reacted 36 hours at 38 DEG C, is obtained intermediate product.
Processing 60 hours is dried in above-mentioned intermediate product under 78 DEG C, vacuum condition, predrying product is obtained；By institute
State predrying product and be heat-treated 6min at 400 DEG C, obtain graphene powder.
The dispersiveness and carbon oxygen mass ratio of the graphene powder obtained according to the method described in embodiment 1 to embodiment 8 are entered
Row detection, testing result is that the lamella stacking degree for the graphene powder that the embodiment of the present invention 8 is obtained is relatively low, and dispersiveness is preferable,
The carbon oxygen mass ratio of graphene powder is 1.2:1.
Embodiment 9
Under conditions of stirring, by phosphoric acid of the 10g granularities for 50 μm of expanded graphite, 300mL fuming nitric aicd and 60mL
First mix, carried out after 140g sodium chlorate and 20g potassium permanganate are added into obtained mixture at 75 DEG C 28 hours
Oxidation reaction, obtains reaction solution.
After above-mentioned reaction solution is stood into 70 hours, potassium hydroxide is added into the reaction solution, makes the reaction molten
The pH value of liquid is 12, and the reaction product in the reaction solution is flocculated, graphite oxide is obtained.
Above-mentioned graphite oxide is washed with water to after neutrality, by the graphite oxide and ammonium carbonate in mass ratio 1:10 ratio
Example is dispersed in water, and is then reacted 48 hours at 25 DEG C, is obtained intermediate product.
Above-mentioned intermediate product is heat-treated 3min at 200 DEG C, graphene powder is obtained.
The dispersiveness and carbon oxygen mass ratio of the graphene powder obtained according to the method described in embodiment 1 to embodiment 9 are entered
Row detection, testing result is that the lamella stacking degree for the graphene powder that the embodiment of the present invention 9 is obtained is relatively low, and dispersiveness is preferable,
The carbon oxygen mass ratio of graphene powder is 1:0.8.
Embodiment 10
Under conditions of stirring, by dense sulphur of the 10g granularities for 100 μm of native graphite, 300mL fuming nitric aicd and 20mL
Acid is first mixed, and is carried out 25 hours at 62 DEG C after 160g potassium chlorate and 20g potassium permanganate are added into obtained mixture
Oxidation reaction, obtain reaction solution.
After above-mentioned reaction solution is stood into 85 hours, potassium hydroxide is added into the reaction solution, makes the reaction molten
The pH value of liquid is 13, and the reaction product in the reaction solution is flocculated, graphite oxide is obtained.
Above-mentioned graphite oxide is washed with water to after neutrality, by the graphite oxide and ammonium sulfate in mass ratio 1:6.5
Ratio is dispersed in water, and is then reacted 24 hours at 18 DEG C, is obtained intermediate product.
Processing 10 hours is dried in above-mentioned intermediate product under 45 DEG C, vacuum condition, predrying product is obtained；By institute
State predrying product and be heat-treated 13min at 450 DEG C, obtain graphene powder.
The dispersiveness and carbon oxygen mass ratio of the graphene powder obtained according to the method described in embodiment 1 to embodiment 10 are entered
Row detection, testing result is, it is relatively low that the lamella of the graphene powder that the embodiment of the present invention 10 is obtained stacks degree, dispersiveness compared with
Good, the carbon oxygen mass ratio of graphene powder is 1:0.6.
The invention provides a kind of preparation method of graphene powder, comprise the following steps：A, by graphite oxide with it is scattered
Agent is reacted, and obtains intermediate product, and the dispersant includes ammonium salt；B, the intermediate product is heat-treated, obtains stone
Black alkene powder.In the present invention, dispersant can reduce the moisture in graphite oxide, it is to avoid graphene oxide is in dehydration
Stronger capillary force is produced in journey, weakens the degree being in close contact between oxidized graphite flake layer, the graphite for obtaining the present invention
The reunion degree of alkene powder is relatively low, dispersed preferable；And the dispersant in the present invention is thermally decomposed during heat treatment
Substantial amounts of gas is produced, the gas of generation can peel off graphite oxide, further reduce the Graphene powder that the present invention is provided
The reunion degree of body, makes the present invention obtain dispersed preferably graphene powder.Compared with prior art, the present invention is without carrying out
Spray drying treatment can prepare dispersed preferably graphene powder, therefore the system of the graphene powder of the invention provided
The low, efficiency high of Preparation Method power consumption, available for large-scale production graphene powder.In addition, the decomposition temperature of the dispersant in the present invention
Degree is relatively low, and the present invention need not carry out high-temperature heat treatment and can remove dispersant, is conducive to controlling what is obtained in heat treatment process
The degree of oxidation of graphene powder, makes the present invention prepare the controllable graphene powder of degree of oxidation.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (5)
1. a kind of preparation method of graphene powder, comprises the following steps：
A, graphite oxide and dispersant reacted, obtain intermediate product, the dispersant is selected from ammonium hydrogen carbonate；Graphite oxide
Mass ratio with dispersant is 1:(1~8)；
B, by the intermediate product carry out pre-dried, obtain predrying product；
The predrying product is heat-treated, graphene powder is obtained；
The temperature being heat-treated in the step b is 80 DEG C~200 DEG C；
The time being heat-treated in the step b is 1min~30min.
2. according to the method described in claim 1, it is characterised in that the reaction temperature reacted in the step a is 15 DEG C~40
℃；
The reaction time reacted in the step a is 24 hours~96 hours.
3. according to the method described in claim 1, it is characterised in that the preparation method of graphite oxide is in the step a：
Graphite is subjected to oxidation reaction, reaction solution is obtained；
The reaction solution is mixed with alkali compounds, the reaction product in the reaction solution is flocculated, obtains aoxidizing stone
Ink.
4. method according to claim 3, it is characterised in that the alkali compounds include sodium carbonate, sodium hydroxide and
One or more in potassium hydroxide.
5. according to the method described in claim 1, it is characterised in that the temperature of the pre-dried is 40 DEG C~80 DEG C；
The time of the pre-dried is 12 hours~96 hours.
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| CN105347331B (en) * | 2015-11-17 | 2017-10-24 | 中南大学 | A kind of method of prepare with scale graphene |
| US10890550B2 (en) * | 2016-08-08 | 2021-01-12 | B.G. Negev Technologies & Applications Ltd. At Ben-Gurion University | High sensitivity broad-target porous graphene oxide capacitive vapor sensor |
| CN117142522A (en) * | 2017-10-12 | 2023-12-01 | 国立大学法人东京工业大学 | Inorganic particle composite, method for producing same, inorganic particle composite dispersion liquid, and composition |
| CN108840333A (en) * | 2018-01-10 | 2018-11-20 | 西北师范大学 | A kind of preparation method of cellular graphite oxide |
| CN113003569B (en) * | 2021-04-28 | 2021-10-29 | 南京工业大学 | Method for preparing reduced graphene oxide powder with high specific surface area |
| CN113429808A (en) * | 2021-06-28 | 2021-09-24 | 成都新柯力化工科技有限公司 | Isolation dispersant for preventing graphene agglomeration, preparation method and application method |
| CN113860300B (en) * | 2021-09-25 | 2024-03-26 | 凯盛石墨碳材料有限公司 | Method for preparing expanded graphite by circulating freezing |
| CN113816371B (en) * | 2021-09-25 | 2023-09-08 | 凯盛石墨碳材料有限公司 | Method for preparing expandable graphite through freeze-drying |
| CN115465855B (en) * | 2022-10-14 | 2023-08-15 | 湖北冠毓新材料科技有限公司 | Solid carbon nano tube dispersing method |
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